Perovskite passivation material, passivation layer film, preparation method of passivation layer film and perovskite solar cell

Abstract

The invention discloses a perovskite passivation material, a passivation layer film, a preparation method of the passivation layer film and a perovskite solar cell, and belongs to the field of photovoltaic technology. The perovskite passivation material comprises a triammonium organic ammonium salt. The preparation method of the perovskite passivation layer film comprises the following steps: S1, mixing a passivation material and a solvent to obtain a passivation solution; and S2, coating the passivation solution on the surface of a perovskite active layer to form the perovskite passivation layer film. By introducing the triammonium organic ammonium salt, the passivation density can be improved, coordination is formed through amino and metal ions on the surface of perovskite, the interface modification capacity is provided, defect titanium on the surface of perovskite is reduced, the interface energy level is improved, non-radiative recombination is reduced, the interface bonding force and structural stability are enhanced, and the passivation quality is further improved; grain growth can be promoted, the light absorptivity is improved, and the photoelectric conversion efficiency of the perovskite solar cell is improved.

Description

Technical Field

[0001] The present invention relates to the field of photovoltaic technology, and in particular to a perovskite passivation material, a passivation layer film and a preparation method thereof, and a perovskite solar cell. Background Art

[0002] Perovskite photovoltaics is an emerging photovoltaic technology that has developed rapidly in recent years. Thanks to the high defect tolerance and solution processability of perovskite photovoltaic materials, the photoelectric conversion efficiency of perovskite solar cells has rapidly increased from 9% to the current more than 26%, and is very suitable for large-area processing.

[0003] At present, the improvement of perovskite efficiency is mainly achieved by using a single passivation material to passivate perovskite surface or bulk defects, inhibit recombination, adjust interface dipoles, etc. The ammonium salts used are all monoammonium or diammonium organic salts. This passivation method can only produce one effect through the passivation material used; or by further chemically modifying the passivation molecules to produce multiple effects through one molecule. However, this method requires further chemical modification of the passivation molecules, which significantly increases the cost. Summary of the invention

[0004] The main purpose of the present invention is to provide a perovskite passivation material, a passivation layer film and a preparation method thereof, and a perovskite solar cell, so as to solve the problem in the prior art that the perovskite passivation layer has limited effect and affects the photoelectric conversion efficiency.

[0005] In order to achieve the above object, according to one aspect of the present invention, a perovskite passivation material is provided, which includes a triammonium organic ammonium salt.

[0006] Furthermore, the cation of the triammonium organic ammonium salt is selected from TEA 3+ ETMA 3+ and TEAPh 3+ At least one of; wherein, TEA 3+ The chemical structural formula is Formula I, ETMA 3+ The chemical structural formula is Formula II, TEAPh 3+ The chemical structural formula is Formula III;

[0007]

[0008] Furthermore, the anion of the triammonium organic ammonium salt is selected from halogen anions.

[0009] Further, the halogen anion is selected from I - Br - , Cl - and F - At least one of .

[0010] Further, the triammonium organic ammonium salt is selected from at least one of 2-ethylammonium-1,3-propanediammonium hydroiodide, 2-ethylammonium-2-methyl-1,3-propanediammonium hydroiodide and 1,3,5-trimethylammoniumbenzene hydroiodide.

[0011] Furthermore, the passivation material also includes monoammonium organic ammonium salt and / or diammonium organic ammonium salt.

[0012] Further, the cation of the monoammonium organic ammonium salt is selected from 3-PyA + 、PEA + and BA + At least one of; wherein 3-PyA + The chemical structural formula is IV, PEA + The chemical structure is Formula V, BA + The chemical structural formula is Formula VI;

[0013]

[0014] Further, the cation of the diammonium organic ammonium salt is PDA 2+ , whose chemical structural formula is Formula VII;

[0015]

[0016] Furthermore, the anions of the monoammonium organic ammonium salt and the diammonium organic ammonium salt are each independently selected from halogen anions or halogen-like anions.

[0017] Further, the halogen anion is selected from I - Br - , Cl - and F - At least one of .

[0018] Furthermore, the halogen-like anion is selected from CN - 、OCN - and SCN - At least one of .

[0019] Furthermore, the monoammonium organic ammonium salt is selected from at least one of 3-picolyl ammonium hydrobromide, phenylethylammonium hydroiodide and butylammonium hydrochloride.

[0020] Furthermore, the diammonium organic ammonium salt is 1,3-propanediammonium hydrochloride.

[0021] Furthermore, the perovskite passivation material is a mixture of triammonium organic ammonium salt and monoammonium organic ammonium salt.

[0022] Furthermore, the mass ratio of the triammonium organic ammonium salt to the monoammonium organic ammonium salt is (1-50):100; furthermore, (5-40):100; furthermore, (10-30):100.

[0023] Furthermore, the perovskite passivation material is a mixture of triammonium organic ammonium salt, monoammonium organic ammonium salt and diammonium organic ammonium salt; wherein the mass ratio of the total mass of the diammonium organic ammonium salt and the triammonium organic ammonium salt to the monoammonium organic ammonium salt is (1-50):100; further (5-40):100; further (10-30):100; wherein the mass ratio of the diammonium organic ammonium salt and the triammonium organic ammonium salt is (1-5):1.

[0024] Furthermore, the perovskite passivation material is a mixture of triammonium organic ammonium salt and diammonium organic ammonium salt.

[0025] Furthermore, the mass ratio of the triammonium organic ammonium salt to the diammonium organic ammonium salt is (1-50):100; further (5-40):100; further (10-30):100.

[0026] According to the second aspect of the present application, a method for preparing the above-mentioned perovskite passivation layer film is provided, comprising the following steps:

[0027] Step S1: mixing a passivation material and a solvent to obtain a passivation solution; wherein the passivation material is the above-mentioned perovskite passivation material;

[0028] Step S2: coating the passivation solution on the surface of the perovskite active layer to form a perovskite passivation layer film.

[0029] Furthermore, the mass concentration of the passivation solution in step S1 is 1% to 99.9%; further 1% to 30%, and further preferably 5% to 20%.

[0030] Furthermore, the solvent is selected from at least one of chlorobenzene, toluene, methanol, ethanol, isopropanol, acetonitrile, phenylethanol, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and γ-butyrolactone.

[0031] According to a third aspect of the present application, a perovskite passivation layer film is provided, which is prepared by the above-mentioned preparation method.

[0032] According to a fourth aspect of the present application, a perovskite solar cell is provided, comprising a glass substrate, a first electrode, a hole transport layer, a perovskite active layer, a passivation layer, an electron transport layer and a second electrode arranged in sequence; or a glass substrate, a first electrode, an electron transport layer, a perovskite active layer, a passivation layer, a hole transport layer and a second electrode are arranged in sequence; wherein the passivation layer is the above-mentioned perovskite passivation layer film.

[0033] Further, the first electrode is selected from at least one of Au, Ag, Cu and Al, and the second electrode is selected from at least one of ITO, IZO and AZO; or, the first electrode is selected from at least one of ITO, IZO and AZO, and the second electrode is selected from at least one of Au, Ag, Cu and Al.

[0034] Furthermore, the electron transport layer is selected from at least one of tin oxide, titanium oxide, zinc oxide, fullerene and its derivatives, graphyne and its derivatives.

[0035] Furthermore, the hole transport layer is selected from at least one of self-assembled monolayer materials, nickel oxide, molybdenum oxide, tungsten oxide, 2,2',7,7'-tetrakis(N,N-dimethylamino)-9,9'-spirobifluorene and poly(3-hexylthiophene).

[0036] Furthermore, the structural formula of the perovskite active layer is ABX3; wherein A is at least one of MA, MDA, FA, PEA, Cs, Rb and K; MA is CH3NH3; MDA is NH3CH2NH3; FA is NH2CHNH2; PEA is C8H9NH3; B is at least one of Pb, Sn and Ge; and X is at least one of F, Cl, Br and I.

[0037] According to a fifth aspect of the present application, a perovskite module device is provided, including a perovskite solar cell, which is the above-mentioned perovskite solar cell.

[0038] Furthermore, the perovskite module device is composed of 3 to 5 groups of perovskite solar cells.

[0039] By applying the technical solution of the present invention, a method for preparing a perovskite passivation material and a passivation layer film is provided. By introducing triammonium organic ammonium salts, the passivation density can be improved, and the coordination effect is formed between amino groups and metal ions on the surface of the perovskite to provide interface modification ability, reduce the defective titanium on the surface of the perovskite, improve the interface energy level, reduce non-radiative recombination, enhance the interface bonding force and structural stability, further improve the passivation quality, promote grain growth, increase light absorption rate, and improve the photoelectric conversion efficiency of perovskite solar cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] The drawings constituting a part of the present application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0041] Figure 1 A schematic diagram of the structure of a perovskite photovoltaic device prepared in an embodiment of the present invention is shown;

[0042] Figure 2A diagram showing the photoelectric conversion efficiency of the ETMAI3-passivated perovskite solar cell in Example 1 of the present invention is shown;

[0043] Figure 3 The photoelectric conversion efficiency diagram of the perovskite solar cell passivated with PEAI:ETMAI3 (5:1 w / w) in Example 5 of the present invention is shown;

[0044] Figure 4 The photoelectric conversion efficiency diagram of the non-passivated perovskite solar cell of Comparative Example 1 of the present invention is shown;

[0045] Figure 5 The photoelectric conversion efficiency diagram of the PEAI-passivated perovskite solar cell in Comparative Example 2 of the present invention is shown. DETAILED DESCRIPTION

[0046] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0047] In traditional technology, monoammonium or diammonium organic ammonium salts are used as passivation materials to passivate the surface defects of perovskite, which are used to passivate the surface or bulk defects of perovskite, inhibit recombination, adjust the interface dipole, etc.; however, the passivation effect of the monoammonium organic ammonium salts is relatively weak and needs to be improved.

[0048] Therefore, the present invention provides a perovskite passivation material, which includes a triammonium organic ammonium salt.

[0049] The present invention selects triammonium organic ammonium salt as the passivation material on the surface of the perovskite active layer. The triammonium organic ammonium salt has three amino groups, which can produce a good coordination effect with the perovskite metal ions, can improve the passivation density and the ability to modify the perovskite interface, can further reduce the defects on the surface of the perovskite active layer, improve the interface ability, reduce non-radiative recombination, enhance the interface bonding force and structural stability, further improve the passivation quality, promote grain growth, improve the light absorption rate, and improve the photoelectric conversion efficiency of the perovskite solar cell.

[0050] In some embodiments, the cation of the triammonium organic ammonium salt is selected from TEA 3+ ETMA 3+ and TEAPh 3+ At least one of; wherein, TEA 3+ The chemical structural formula is Formula I, ETMA 3+ The chemical structural formula is Formula II, TEAPh 3+ The chemical structural formula is Formula III;

[0051]

[0052] The anion of the triammonium organic ammonium salt is selected from halogen anions, for example, the halogen anions are selected from at least one of I-, Br-, Cl- and F-; specifically, the triammonium organic ammonium salt includes 2-ethylammonium-1,3-propanediammonium (TEA 3+ ) halide salts, 2-ethylammonium-2-methyl-1,3-propanediammonium (ETMA 3+ ) and 1,3,5-trimethylammoniumbenzene (TEAPh 3+ The halide salt includes iodine salt, bromide salt or chloride salt.

[0053] For example:

[0054] For another example, the triammonium organic ammonium salt is at least one selected from 2-ethylammonium-1,3-propanediammonium hydroiodide, 2-ethylammonium-2-methyl-1,3-propanediammonium hydroiodide and 1,3,5-trimethylammoniumbenzene hydroiodide.

[0055] The above-mentioned triammonium organic ammonium salts of the present invention all contain three amino groups, which have a stronger coordination effect with the perovskite metal, can enhance the passivation density, further increase the structural stability, further improve the surface defects of the perovskite, and can further improve the passivation quality and the photoelectric efficiency.

[0056] In some embodiments, the passivation material further comprises a monoammonium organic ammonium salt and / or a diammonium organic ammonium salt.

[0057] The present invention mainly uses triammonium organic ammonium salts and combines them with monoammonium and / or diammonium salts; wherein the triammonium organic ammonium salts are used to passivate the defects on the surface of the perovskite active layer or at the perovskite grain boundary, and the monoammonium and / or diammonium organic ammonium salts are used to strengthen the defect passivation and provide interface dipole modification capability; the present invention can enhance the passivation effect and further improve the photoelectric conversion efficiency of the perovskite solar cell by combining the triammonium organic ammonium salts with the monoammonium / diammonium organic ammonium salts.

[0058] In some embodiments, the cation of the monoammonium organic ammonium salt is selected from 3-PyA + (3-pyridiniummethylammonium), PEA + (phenylethylammonium) and BA + (butylammonium) one or more; the cation of the diammonium organic ammonium salt is PDA 2+ (1,3-propanediammonium); the anion of the monoammonium organic ammonium salt and / or the anion of the diammonium organic ammonium salt is selected from I - Br - , Cl - 、F - , halogen-like anions CN - 、OCN - and SCN - One or more of .

[0059] For example: the cation of the monoammonium organic ammonium salt is selected from 3-PyA + 、PEA + and BA + At least one of; wherein 3-PyA + The chemical structural formula is IV, PEA + The chemical structure is Formula V, BA + The chemical structural formula is Formula VI;

[0060]

[0061] The cation of diammonium organic ammonium salt is PDA 2+ , whose chemical structural formula is Formula VII;

[0062]

[0063] For example:

[0064] The anion of the monoammonium organic ammonium salt is selected from halogen anions or quasi-halogen anions; the anion of the diammonium organic ammonium salt is selected from halogen anions or quasi-halogen anions; the halogen anions are selected from I - Br - , Cl - and F - At least one of; the halogen-like anion is selected from CN - 、OCN - and SCN - At least one of .

[0065] For example, the monoammonium organic ammonium salt is selected from at least one of 3-picolyl ammonium hydrobromide, phenylethylammonium hydroiodide and butylammonium hydrochloride; the diammonium organic ammonium salt is 1,3-propanediammonium hydrochloride.

[0066] In the present invention, the above-mentioned monoammonium and diammonium organic ammonium salts firstly have a certain perovskite passivation ability themselves, and the passivation effect is weak when used alone, but when the mono / diammonium organic ammonium salts and triammonium organic ammonium salts are used in combination, they have better synergistic effects. When triammonium and monoammonium, triammonium and diammonium, triammonium and diammonium and monoammonium are used in combination, they have better synergistic effects, the passivation effect is significantly improved, and no side effects such as mutual influence will occur.

[0067] The present invention uses triammonium organic ammonium salt and other ammonium salts in combination as follows:

[0068] In some embodiments, when the perovskite passivation material is a mixture of triammonium organic ammonium salt and monoammonium organic ammonium salt, the mass ratio of the triammonium organic ammonium salt to the monoammonium organic ammonium salt is (1-50):100; further (5-40):100; further (10-30):100; for example, 1:100, 5:100, 10:100, 15:100, 20:100, 25:100, 30:100, 35:100, 40:100, 45:100, 50:100.

[0069] According to the structural characteristics and the number of amino groups of monoammonium and triammonium organic ammonium salts and the synergistic passivation effect exerted by them, the present invention adjusts the use ratio of the two to (10-30):100 to obtain a better perovskite passivation effect without wasting materials.

[0070] In some embodiments, when the perovskite passivation material is a mixture of triammonium organic ammonium salt, monoammonium organic ammonium salt and diammonium organic ammonium salt, the mass ratio of the total mass of the diammonium organic ammonium salt and the triammonium organic ammonium salt to the monoammonium organic ammonium salt is (1-50):100; further (5-40):100; further (10-30):100; for example, 1:100, 5:100, 10:100, 15:100, 20:100, 25:100, 30:100, 35:100, 40:100, 45:100, 50:100; wherein the mass ratio of the diammonium organic ammonium salt to the triammonium organic ammonium salt is (1-5):1.

[0071] When the mono-, di- and tri-ammonium organic ammonium salts are used in combination, the three introduce a relatively large amino density, and a suitable use ratio needs to be regulated to fully exert their respective passivation capabilities and improve the passivation effect, without causing side reactions and also saving materials.

[0072] In some embodiments, when the perovskite passivation material is a mixture of triammonium organic ammonium salt and diammonium organic ammonium salt, the mass ratio of the triammonium organic ammonium salt to the diammonium organic ammonium salt is (1-50):100; further (5-40):100; further (10-30):100; for example, 1:100, 5:100, 10:100, 15:100, 20:100, 25:100, 30:100, 35:100, 40:100, 45:100, 50:100. The present invention optimizes the mixing ratio according to the diammonium structural characteristics and the triammonium structural characteristics, thereby achieving improved passivation effect without wasting materials.

[0073] In the above-mentioned combination scheme of the present application, although the proportion of triammonium organic ammonium salt is relatively small, it can provide a better passivation effect, while the proportion of monoammonium and diammonium is relatively large. Due to their structural characteristics, only when the above-mentioned proportion is adjusted and used in combination with triammonium organic ammonium salt can a better passivation effect be achieved; when the proportion of triammonium organic ammonium salt in the mixed ammonium salt is too large, it will cause material waste, and may accumulate on the surface of perovskite, resulting in defects and reducing the photoelectric efficiency. If the proportion of triammonium is too small, it cannot effectively achieve a better passivation effect.

[0074] According to a second aspect of the present invention, a method for preparing a perovskite passivation layer film is provided, comprising the following steps:

[0075] Step S1: mixing the above passivation material and a solvent to obtain a passivation solution;

[0076] Step S2: coating the passivation solution on the surface of the perovskite active layer to form a perovskite passivation layer film.

[0077] The present invention forms a passivation layer film on the active surface of the perovskite by coating the developed passivation solution on the active surface of the perovskite. The amino groups of the passivation material and the metal ions of the perovskite active material produce a good coordination effect, thereby enhancing the interface bonding force. The passivation material can reduce the surface defects of the perovskite, improve the interface energy level, enhance the interface modification ability, reduce non-radiative recombination, further improve the passivation quality, promote grain growth, increase light absorption rate, and improve the photoelectric conversion efficiency of the perovskite solar cell.

[0078] In some embodiments, the mass concentration of the passivation solution in step S1 is 1% to 99.9%; further the mass concentration is 1% to 50%; further the mass concentration is 1% to 30%; further 5% to 20%; for example 5% to 15%, 5% to 20%, 5% to 30%, 5% to 40%, 5% to 50%; specifically 1%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99% or any range of any two of them.

[0079] The present invention controls the concentration of the passivation solution to be between 1% and 30%, so that the organic ammonium salt can more appropriately exert its passivation ability and improve the passivation effect. When the concentration of the passivation solution is too high, it is easy to aggregate on the surface of the perovskite active layer to form defects, which will reduce the photoelectric efficiency. When the concentration is too low, the passivation effect cannot be effectively exerted. Therefore, the concentration of the passivation solution also has a certain influence on the passivation effect of the perovskite, and needs to be adjusted to a suitable concentration range.

[0080] In some embodiments, the solvent is selected from one or more of chlorobenzene, toluene, methanol, ethanol, isopropanol, acetonitrile, phenylethanol, DMF, DMSO, NMP and γ-GBL. The above solvents selected in the present invention have good compatibility with the above organic ammonium salts, and other types of organic solvents can also be selected from the prior art.

[0081] In some embodiments, the coating method may be spin coating, scraper coating, or spray coating; other suitable coating methods may also be selected from the prior art.

[0082] According to a third aspect of the present invention, a perovskite passivation layer film is provided, which is prepared by the above-mentioned preparation method.

[0083] According to a fourth aspect of the present invention, a perovskite solar cell is provided, comprising a glass substrate, a first electrode, a hole transport layer, a perovskite active layer, a passivation layer, an electron transport layer and a second electrode arranged in sequence; or a glass substrate, a first electrode, an electron transport layer, a perovskite active layer, a passivation layer, a hole transport layer and a second electrode; wherein the passivation layer comprises the above-mentioned perovskite passivation layer film.

[0084] In some embodiments, the first electrode is selected from at least one of Au, Ag, Cu and Al, and the second electrode is selected from at least one of ITO, IZO and AZO; or, the first electrode is selected from at least one of ITO, IZO and AZO, and the second electrode is selected from at least one of Au, Ag, Cu and Al; the electron transport layer is selected from one or more of tin oxide, titanium oxide, zinc oxide, fullerene and its derivatives, graphyne and its derivatives; the hole transport layer is selected from at least one of self-assembled monolayer materials SAMs (Self-Assembled Monolayers), nickel oxide, molybdenum oxide, tungsten oxide, Spiro-OMeTAD (2,2',7,7'-tetrakis-(N,N-di methylamino)-9,9'-spirobifluorene, 2,2',7,7'-tetrakis-(N,N-dimethylamino)-9,9'-spirobifluorene) and PTAA (Poly(3-hexylthiophene), poly(3-hexylthiophene)). The structural formula of the perovskite active layer is ABX3; wherein A is one or more of MA, MDA, FA, PEA, Cs, Rb and K; MA is CH3NH3; MDA is NH3CH2NH3; FA is NH2CHNH2; PEA is C8H9NH3; B is one or more of Pb, Sn and Ge; and X is one or more of F, Cl, Br and I.

[0085] The passivation material and the passivation layer film prepared in the present invention are suitable for the passivation process of more types of perovskite active layers, and are not limited to the type of perovskite active material ABX3. In addition to the above-mentioned perovskite active layer, the passivation material of the present invention not only has a good passivation effect on the above-mentioned perovskite active layer, but also the passivation layer film prepared therefrom has good bonding and functional matching with the adjacent electron transport layer or hole transport layer, and is suitable for the manufacture of perovskite solar cells.

[0086] According to a fourth aspect of the present invention, a perovskite module device is provided, including a perovskite solar cell; the perovskite solar cell is the above-mentioned perovskite solar cell; the specific perovskite module device can be composed of 3 to 5 groups of perovskite solar cells.

[0087] The present application is further described in detail below in conjunction with specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in the present application.

[0088] The raw materials used in the embodiments of the present invention are available from the prior art and are commercially available.

[0089] For example: 2-ethylammonium-1,3-propanediammonium hydroiodide (TEAI3), 2-ethylammonium-2-methyl-1,3-propanediammonium hydroiodide (ETMAI3), 1,3,5-trimethylammoniumbenzene hydroiodide (TEAPhI3), 1,3-propanediammonium hydrochloride (PDACl2), 3-picolylammonium hydrobromide (3-PyABr), phenylethylammonium hydroiodide (PEAI), butylammonium hydrochloride (BACl).

[0090] Example 1

[0091] A method for preparing a perovskite passivation layer film comprises the following steps:

[0092] Step S1: 10 mg of 2-ethylammonium-2-methyl-1,3-propanediammonium hydroiodide (ETMAI3) and ethanol were mixed to prepare a passivation solution with a concentration of 10%;

[0093] Step S2: Spin-coat the passivation solution onto the surface of the FAPbI3 (FA is NH2CHNH2) perovskite active layer, place the sample on a heating table for annealing to form a perovskite passivation layer film, and the annealing temperature is 100°C.

[0094] Example 2

[0095] A method for preparing a perovskite passivation layer film comprises the following steps:

[0096] Step S1: 20 mg of 1,3,5-trimethylammoniumbenzene hydroiodide (TEAPhI3) and methanol are mixed to prepare a passivation solution with a mass concentration of 20%;

[0097] Step S2: Spin-coat the passivation solution onto the surface of the FAPbI3 (FA is NH2CHNH2) perovskite active layer, place the sample on a heating table for annealing to form a perovskite passivation layer film, and the annealing temperature is 110°C.

[0098] Example 3

[0099] A method for preparing a perovskite passivation layer film comprises the following steps:

[0100] Step S1: 30 mg of 2-ethylammonium-1,3-propanediammonium hydroiodide (TEAI3) and N,N-dimethylformamide were mixed to obtain a passivation solution with a mass concentration of 30%;

[0101] Step S2: Spin-coat the passivation solution onto the surface of the FAPbI3 (FA is NH2CHNH2) perovskite active layer, place the sample on a heating table for annealing to form a perovskite passivation layer film, and the annealing temperature is 120°C.

[0102] Example 4

[0103] A method for preparing a perovskite passivation layer film comprises the following steps:

[0104] Step S1: 2-ethylammonium-1,3-propanediammonium hydroiodide (TEAI3) and 3-pyridinium hydrobromide (3-PyABr) were mixed at a mass ratio of 10 mg:100 mg, and then mixed with methanol to obtain a passivation solution with a mass concentration of 30%;

[0105] Step S2: Spin-coat the passivation solution onto the surface of the FAPbI3 (FA is NH2CHNH2) perovskite active layer, place the sample on a heating table for annealing to form a perovskite passivation layer film, and the annealing temperature is 110°C.

[0106] Example 5

[0107] A method for preparing a perovskite passivation layer film comprises the following steps:

[0108] Step S1: 2-ethylammonium-2-methyl-1,3-propanediammonium hydroiodide (ETMAI3) and phenylethylammonium hydroiodide (PEAI) are mixed at a mass ratio of 20 mg:100 mg, and then mixed with methanol to obtain a passivation solution with a mass concentration of 10%;

[0109] Step S2: Spin-coat the passivation solution onto the surface of the FAPbI3 (FA is NH2CHNH2) perovskite active layer, place the sample on a heating table for annealing to form a perovskite passivation layer film, and the annealing temperature is 110°C.

[0110] Example 6

[0111] A method for preparing a perovskite passivation layer film comprises the following steps:

[0112] Step S1: 1,3,5-trimethylammoniumbenzene hydroiodide (TEAPhI3) and butylammonium hydrochloride (BACl) are mixed at a mass ratio of 30 mg:100 mg, and then mixed with isopropanol to prepare a passivation solution with a mass concentration of 20%;

[0113] Step S2: Spin-coat the passivation solution onto the surface of the FAPbI3 (FA is NH2CHNH2) perovskite active layer, place the sample on a heating table for annealing to form a perovskite passivation layer film, and the annealing temperature is 110°C.

[0114] Example 7

[0115] A method for preparing a perovskite passivation layer film comprises the following steps:

[0116] Step S1: 2-ethylammonium-1,3-propanediammonium hydroiodide (TEAI3) and 1,3-propanediammonium hydrochloride (PDACl2) are mixed at a mass ratio of 20 mg:100 mg, and then mixed with isopropanol to prepare a passivation solution with a mass concentration of 15%;

[0117] Step S2: Spin-coat the passivation solution onto the surface of the FAPbI3 (FA is NH2CHNH2) perovskite active layer, place the sample on a heating table for annealing to form a perovskite passivation layer film, and the annealing temperature is 110°C.

[0118] Example 8

[0119] A method for preparing a perovskite passivation layer film comprises the following steps:

[0120] Step S1: 2-ethylammonium-1,3-propanediammonium hydroiodide (TEAI3), 1,3-propanediammonium hydrochloride (PDACl2), and phenylethylammonium hydroiodide (PEAI) are mixed in a mass ratio of 5 mg:5 mg:100 mg, and then mixed with ethanol to prepare a passivation solution with a mass concentration of 30%;

[0121] Step S2: Spin-coat the passivation solution onto the surface of the FAPbI3 (FA is NH2CHNH2) perovskite active layer, place the sample on a heating table for annealing to form a perovskite passivation layer film, and the annealing temperature is 110°C.

[0122] Example 9

[0123] The difference between Example 9 and Example 8 is that, step S1: 2-ethylammonium-2-methyl-1,3-propanediammonium hydroiodide (ETMAI3), 1,3-propanediammonium hydrochloride (PDACl2), and 3-pyridiniummethylammonium hydrobromide (3-PyABr) are mixed in a mass ratio of 10 mg: 10 mg: 100 mg, and then mixed with ethanol to prepare a passivation solution with a mass concentration of 20%;

[0124] Example 10

[0125] The difference between Example 10 and Example 8 is that, step S1: 1,3,5-trimethylammoniumbenzene hydroiodide (TEAPhI3), 1,3-propanediammonium hydrochloride (PDACl2), and butylammonium hydrochloride (BACl) are mixed in a mass ratio of 15 mg: 15 mg: 100 mg, and then mixed with ethanol to obtain a passivation solution with a mass concentration of 10%.

[0126] Embodiment 11

[0127] The difference between Example 11 and Example 8 is that, step S1: 1,3,5-trimethylammoniumbenzene hydroiodide (TEAPhI3), 1,3-propanediammonium hydrochloride (PDACl2), and butylammonium hydrochloride (BACl) are mixed in a mass ratio of 10 mg:40 mg:100 mg, and then mixed with ethanol to obtain a passivation solution with a mass concentration of 5%.

[0128] Example 12

[0129] The difference between Example 12 and Example 8 is that, step S1: 1,3,5-trimethylammoniumbenzene hydroiodide (TEAPhI3), 1,3-propanediammonium hydrochloride (PDACl2), and butylammonium hydrochloride (BACl) are mixed in a mass ratio of 3mg:2mg:100mg, and then mixed with ethanol to obtain a passivation solution with a mass concentration of 50%.

[0130] Comparative Example 1

[0131] The difference between Comparative Example 1 and Example 1 is that the surface of the perovskite active layer is not coated with a passivation material; the FAPbI3 perovskite active layer is obtained by spin coating and annealing, and its surface is not treated in any way.

[0132] Comparative Example 2

[0133] The difference between Comparative Example 2 and Example 1 is that the passivation material uses only monoammonium organic ammonium salt; specifically comprising:

[0134] Step S1: Phenethylammonium iodide (PEA +) and ethanol to prepare a passivation solution with a concentration of 10%;

[0135] Step S2: spin-coating the passivation solution onto the surface of the FAPbI3 perovskite active layer to form a perovskite passivation layer film.

[0136] Application Examples

[0137] A perovskite solar cell comprises a glass substrate, a first electrode (ITO), an electron transport layer (tin oxide), a perovskite active layer (FAPbI3), a passivation layer, a hole transport layer (spiro-OMeTAD) and a second electrode (Au) which are arranged in sequence; wherein the passivation layer can be replaced by the passivation layer prepared by the methods of Examples 1 to 12 and Comparative Examples 1 to 2, respectively; 14 different perovskite solar cells are obtained respectively; 14 different perovskite solar cells are selected in sequence (5 cells of the same type form a module) to make a perovskite micromodule device, and the photoelectric performance thereof is tested, and the test results are shown in Table 1. Figure 1 , Figure 2 , Figure 3 , Figure 4 and Figure 5 shown.

[0138] The test method is: under room temperature, using a 3A solar simulator at 100mW / cm 2 The photoelectric conversion efficiency of the micro-modules prepared in the embodiment and the comparative example was tested under different light intensities.

[0139] Table 1

[0140]

[0141]

[0142] The test data in Table 1 show that Examples 1 to 12 of the present invention use triammonium organic ammonium salts to passivate the perovskite active layer, and the photoelectric conversion efficiency of the perovskite battery module prepared therefrom is detected to be about 22.5% to 25%; Comparative Example 1 is a perovskite layer with no passivation film layer on the surface, and the photoelectric conversion efficiency is 19.8%; Comparative Example 2 uses only monoammonium organic ammonium salts as passivation materials, and the photoelectric conversion efficiency of the battery module prepared therefrom is 22.1%; It is obvious that the photoelectric conversion efficiency of the battery module corresponding to the perovskite active layer passivated with triammonium organic ammonium salts of the present invention is as high as 25%, which is increased by about 5%.

[0143] By comparing Examples 1 to 3 with Comparative Example 1, it can be seen that the photoelectric conversion efficiency of the battery module prepared by the present invention using triammonium organic ammonium salt to passivate the perovskite active layer can be increased by about 3%.

[0144] By comparing Examples 4 to 6 with Comparative Example 2, it can be seen that the present invention uses triammonium organic ammonium salts and monoammonium organic ammonium salts in a specific ratio to jointly passivate the perovskite for activation, and the photoelectric conversion efficiency of the prepared battery module can be increased by about 2%, which is about 5% higher than the photoelectric conversion rate of Comparative Example 1.

[0145] By comparing Example 7 and Comparative Example 2, it can be seen that the present invention uses triammonium organic ammonium salts and diammonium organic ammonium salts in a specific ratio to jointly activate the passivated perovskite, and the photoelectric conversion efficiency of the prepared battery module can be increased by about 1%, which is about 3% higher than the photoelectric conversion rate of Comparative Example 1.

[0146] By comparing Examples 8 to 12 with Comparative Example 2, it can be seen that the present invention uses three types of ammonium salts, namely triammonium organic ammonium salts, monoammonium organic ammonium salts and diammonium organic ammonium salts, to jointly passivate the perovskite for activation, and the photoelectric conversion efficiency of the prepared battery module can be increased by about 1.5% to 2.1%, which is about 4% higher than the photoelectric conversion rate of Comparative Example 1.

[0147] Among them, in Examples 4 to 10, when triammonium organic ammonium salts, diammonium organic ammonium salts, and monoammonium organic ammonium salts are used in combination, the mass ratio of the total amount of triammonium organic ammonium salts and diammonium organic ammonium salts to the monoammonium organic ammonium salt is (10 to 30):100, and when the mass concentration of the perovskite passivation solution is 10% to 30%, the photoelectric conversion efficiency of the prepared battery module is relatively higher.

[0148] It should be noted that the terms "first", "second", etc. in the specification and claims of the present application are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the terms used in this way can be interchangeable where appropriate, so that the embodiments of the present application described herein can be implemented in an order other than those described herein, for example.

[0149] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A perovskite passivation material, characterized in that: The perovskite passivation material includes triammonium organic ammonium salt.

2. The perovskite passivation material according to claim 1, characterized in that: The cation of the triammonium organic ammonium salt is selected from TEA 3+ ETMA 3+ and TEAPh 3+ At least one of; wherein the TEA 3+ The chemical structural formula is Formula I, the ETMA 3+ The chemical structural formula is Formula II, wherein the TEAPh 3+ The chemical structural formula is Formula III; Preferably, the anion of the triammonium organic ammonium salt is selected from halogen anions; Preferably, the halogen anion is selected from I - Br - , Cl - and F - At least one of; Preferably, the triammonium organic ammonium salt is selected from at least one of 2-ethylammonium-1,3-propanediammonium hydroiodide, 2-ethylammonium-2-methyl-1,3-propanediammonium hydroiodide and 1,3,5-trimethylammoniumbenzene hydroiodide.

3. The perovskite passivation material according to claim 1 or 2, characterized in that: The passivation material also includes monoammonium organic ammonium salt and / or diammonium organic ammonium salt; Preferably, the cation of the monoammonium organic ammonium salt is selected from 3-PyA + 、PEA + and BA + At least one of; wherein the 3-PyA + The chemical structural formula is Formula IV, the PEA + The chemical structural formula is Formula V, wherein BA + The chemical structural formula is Formula VI; Preferably, the cation of the diammonium organic ammonium salt is PDA 2+ , whose chemical structural formula is Formula VII; Preferably, the anions of the monoammonium organic ammonium salt and the diammonium organic ammonium salt are each independently selected from halogen anions or halogen-like anions; Preferably, the halogen anion is selected from I - Br - , Cl - and F - At least one of; Preferably, the halogen-like anion is selected from CN - 、OCN - and SCN - At least one of; Preferably, the monoammonium organic ammonium salt is selected from at least one of 3-picolyl ammonium hydrobromide, phenylethylammonium hydroiodide and butylammonium hydrochloride; Preferably, the diammonium organic ammonium salt is 1,3-propanediammonium hydrochloride.

4. The perovskite passivation material according to claim 3, characterized in that: The perovskite passivation material is a mixture of the triammonium organic ammonium salt and the monoammonium organic ammonium salt; Preferably, the mass ratio of the triammonium organic ammonium salt to the monoammonium organic ammonium salt is (1-50):100; more preferably (5-40):100; and even more preferably (10-30):100; Preferably, the perovskite passivation material is a mixture of the triammonium organic ammonium salt, the monoammonium organic ammonium salt and the diammonium organic ammonium salt; wherein the mass ratio of the total mass of the diammonium organic ammonium salt and the triammonium organic ammonium salt to the monoammonium organic ammonium salt is (1-50):100; further preferably (5-40):100; further preferably (10-30):100; wherein the mass ratio of the diammonium organic ammonium salt to the triammonium organic ammonium salt is (1-5):1; Preferably, the perovskite passivation material is a mixture of the triammonium organic ammonium salt and the diammonium organic ammonium salt; Preferably, the mass ratio of the triammonium organic ammonium salt to the diammonium organic ammonium salt is (1-50):100; more preferably (5-40):100; and even more preferably (10-30):

100.

5. A method for preparing a perovskite passivation layer film, characterized in that: The preparation method comprises the following steps: Step S1: mixing a passivation material and a solvent to obtain a passivation solution; wherein the passivation material is the perovskite passivation material according to any one of claims 1 to 4; Step S2: coating the passivation solution on the surface of the perovskite active layer to form the perovskite passivation layer film.

6. The method for preparing a perovskite passivation layer film according to claim 5, characterized in that: The mass concentration of the passivation solution in step S1 is 1% to 99.9%; preferably 1% to 30%; more preferably 5% to 20%; And / or, the solvent is selected from at least one of chlorobenzene, toluene, methanol, ethanol, isopropanol, acetonitrile, phenylethanol, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and γ-butyrolactone.

7. A perovskite passivation layer film, characterized in that: The perovskite passivation layer film is prepared by the preparation method described in claim 5 or 6.

8. A perovskite solar cell, characterized in that: It comprises a glass substrate, a first electrode, a hole transport layer, a perovskite active layer, a passivation layer, an electron transport layer and a second electrode arranged in sequence; or a glass substrate, a first electrode, an electron transport layer, a perovskite active layer, a passivation layer, a hole transport layer and a second electrode are arranged in sequence; wherein the passivation layer is the perovskite passivation layer film according to claim 7.

9. The perovskite solar cell according to claim 8, characterized in that: The first electrode is selected from at least one of Au, Ag, Cu and Al, and the second electrode is selected from at least one of ITO, IZO and AZO; or, the first electrode is selected from at least one of ITO, IZO and AZO, and the second electrode is selected from at least one of Au, Ag, Cu and Al; And / or, the electron transport layer is selected from at least one of tin oxide, titanium oxide, zinc oxide, fullerene and its derivatives, graphyne and its derivatives; And / or, the hole transport layer is selected from at least one of a self-assembled monolayer material, nickel oxide, molybdenum oxide, tungsten oxide, 2,2',7,7'-tetrakis(N,N-dimethylamino)-9,9'-spirobifluorene and poly(3-hexylthiophene); And / or, the structural formula of the perovskite active layer is ABX3; wherein A is at least one of MA, MDA, FA, PEA, Cs, Rb and K; MA is CH3NH3; MDA is NH3CH2NH3; FA is NH2CHNH2; PEA is C8H9NH3; B is at least one of Pb, Sn and Ge; X is at least one of F, Cl, Br and I.

10. A perovskite module device, comprising a perovskite solar cell, characterized in that: The perovskite solar cell is the perovskite solar cell according to claim 8 or 9; Preferably, the perovskite module device is composed of 3 to 5 groups of the perovskite solar cells.

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